Calcination of barium carbonate



Dec. 4,1956 Hiw. RAHN ETAL -2,772,949 CALCINATION oF BARIUMI-CARBONTE Filed June 7. 1952 ductV heat.

y 2,772,949 l CALCINATION or BARIUM cARBoNATE Henry W. Rahn and Charles `Lsilldlinger, Corpus Christi,

Tex., assignors to Columbia-Southern Chemical Corporation Application .lune 7V, 195.2, Serial No. 292,284

2 Claims. A(Cl. l23186) This inventionV relates to the ealcination of barium carbonate.l According to a `copending application for United States Letters Patentof Henry W. Rahnand Charles Sindlinger, Serial No. 279,786, led'fApril l,

v1952, methods of calcining barium carbonate are de- Patented Dec. 4, 1956 ,One effective method of establishing the desired `coating involves calcination of barium carbonate granules in a iluidized bed under scale or film-forming conditions. Y

For example, the elemental oxygen or moisture content of nitrogenfused as the uidizing gas may be adjusted to'a'point where scale formation is promoted, for example, l or 2 percent by volume. Calcination of barium carbonate is conducted under these conditions for a suitable period of time, usually not more than 30 to` 60 niinutes.` Since operation under these conditions for an extended Vperiod is objectionable since it causes excessive scale formation, the conditions of calcination are adjusted within a short time so that the moisture and/oroxygen content of the uidizing gas is below 0.5 and preferably below about 0.1 to 0.2 percent by volume. Thereafter,

' calcination is continued under these conditions so that barium oxide, preferably in the form of granules, and Y adding barium carbonate granules thereto while heating the bed and maintaining the barium oxide content thereof sufficiently high to prevent fusion of the bed.

In thepractice of` such a process, it is necessary to supply substantial heat to the bed. This cannot be accomplished by burning fuel in the bed since carbon dioxide evolved during the burning reverses the calcination reaction. Accordingly, the required heatmust be supplied through the walls of thel furn-ace enclosing the bed."

The -fact that heat must'be so supplied makes it important 'that the furnace walls be constructed. of metal since nonmetallic refractory materials do not readily coni However, metal tends to be scoured and corroded in use because of the corrosive character of the barium oxide. Moreover, carbon deposits on themetal walls forming carbides, thus causing embrittlemventof the metal.

vAccording to the present invention, it has been found that these diiculties may be appreciably minimized by calciningv the barium carbonate-in `a `metalV reactor the jexposed `walls of which are coated with a` thin film of 'fused barium oxide or a mixture of barium ,oxide and barium` carbonate. This film Vmust be quite thin since otherwise the conductivity of heat through the walls be comes inefficient. In general, the thickness of this coat- Vand barium carbonate, for example,l Vby applying a liquid 'ing should not exceed` 1A; inch, and preferably should be "0.001 to 0.01 inch in thickness.

suspensionr ofthese materials in-a volatile solvent, such 1* as naphtha, tothe metal walls. 'The metal maythen be heated to 1000 C. to cause 4thecoating to adhere.

Theltemperature of heating should besuicien'tly high' to burn (the coating into themetalor to cause it tofuse or cloalesce into an adherent film. @Since barium oxide forms a eutectic with barium carbonate which melts vat ,a temperature .below that at which ,i either barium oxide Vor barium carbonatejmelts, Vitis preferred to` use a mixture inthe proportion of about 0.5,'.to 4'moles, preferably Vstoichiometric amount of carbon.

littlevor no further film-formation occurs. Best results are achieved when the oxygen content of the fluidizing gas is below 0.01 percent by volume. 'This may be accomplished by mixing hydrogen with nitrogen or other gas to be used in the uidizing 4and passing the mixture over a catalyst to cause the hydrogen to react with oxygen, producing water which may be removed by drying if necessary.

Metals to be used in construction of the reactor must be capable of withstanding the temperatures of operation, i. e., 900 to 1200" C. or above. Typical metal alloys useful `for this purpose are various resistant stainless steels, corrosion resistant nickel alloys, and the like.

The metal alloy which is especially suitable isv that known as Inconel manufactured by International Nickel Company. This alloy contains `7 percent iron and 1`4 percent chromium, the balance being largely nickel. Also p resent are small percentages of carbon, manganese, and silica.

The calcination of the barium carbonate normally is conductedA in the presence of a carbonaceous reducing n agent,` such as carbon, which reacts with the carbonate to liberate carbon monoxide. f

Where it is intended to produce barium peroxide from theresulting barium oxide, the amount of carbon which may beused should not bev excessive. |Ihe theoretical amount of carbon required to react with the barium carbonate to produce barium oxide and carbon monoxide is about 6 percent by weightl of the bariumncarbonate. Where the carbon concentration exceeds more vthan about 6 percent, there exists a tendency for the car bon'to remain in thebarium oxide product produced.

When this product isheated in air or oxygen in order to `produce barium peroxide, the residual carbon reacts to form carbon dioxide. wit-h consequent production of barium carbonate. Such reaction, of course, tends to i defeat the purpose ofthe process. On the other hand, it is usually" impossible to operate with exactly the Consequently, an amount of carbon of about 6v to S percent, based upon the barium carbonate in the composition, normally is used.

in the range of Y 1.5 to 3`fmoles o`f"barium carbonate `per mole of barium oxide." In such a case,`heating the coated -metal to a temperature-of900 to 1100`lC.ffor'a l `few minutes will be sufcient to bondwand fuse-the coating. HigherV temperatures may-` be requiredf-where"` the barium carbonate content'fof the coating is It shouldl be understood that higherrconcentrations 'of carbon may be usedV where the barium oxide is to be use'd for purposes other than the production of barium j peroxide. Moreoven-evenwhere the barium oxide is to beus'ed for barium peroxide, such higher carbon concen- 800 to 1100 C. while'passing a mixture of nitrogen or Iike'inert gas and oxygen, whichvmixture containsless than 20` percent by.volume `of, oxygen. `Such a process may be, usedfto 'materially reduce the carbon concentra.-

"tion of the barium carbonatewithout excessive formation of barium carbonate. The barium oxide thus treated may be subjected to peroxidation without diiiculty. Furthermore, barium oxide may be produced for other purposes using :higher concentrations of carbon, forexarnple, up to..2O percent for more of .the weight of the barium carbonate. Such larger concentrations tend to .reduce or minimize fusion problems.

In the calcination of barium carbonate, serious fusion problems arise,.probably due to the tendency ,to form a barium oxide-.barium carbonate .eutectio 'Whatever the cause, the tendency toward Afusion may be minimized by .maintaining the barium oxide content ofthe bed undergoing calcination above that of the low melting Ypoint .eutectic `which has the approximate BaO2BaCO3.

Y This may be accomplished, for example, by establishing .afbed heated .to calcination vten'iperature and containing `at 'least 50 to 75 percentLand preferably in excess of .90 percent, by weight of barium oxide, and adding barium .carbonate thereto while withdrawing barium oxide, the .rates of addition and withdrawal being such lthat the BaO ,content ofthe bed does not fall below about 50 percent for an appreciable period, and preferably remains above 90 percent by weight during the calcination. Alternatively, barium oxide may be mixed with barium carbonate .in amounts equal to 50 percent or more of the barium carbonate-barium oxide content of the mixture, and the mixture introduced into the calcination zone. By recourse to this procedure, the fusion or sintering encountered in prior processes is avoided or minimized Yto a degree suicient to permit flow of the material through arcalcination zone and, thus, the process may be conducted in acontinuous or semi-continuous manner. v,Atypicalembodiment of a method of practicing this invention and theY apparatus contemplated according to "this invention are iilustrated diagrammatically in the .accompanying drawing.

compositionA ln order to avoid excessive production of dustV andV .toensure establishment of a iluidized bed, it is desired to .calcine granules of barium carbonate which are of substantial size. Nitrogen or vlike inert gas is requiredjto t promote calcina'tio-n of barium carbonate and to dilute ,evolved carbon monoxide, thus to reduce its partial pres- .sure and to increase the rate of reaction. It has been found ,that the required gas veiocity is sohigh that barium .carbonate which has a particle size smaller than about ,8O ,mesh ldoers not readily form a iluidized bed. Consequently,v the greater portion of thebarium carbonate to betrea'ted'shouldbe of a particle size greater than 8O mesh The V.maximum -particle size depends .to some .degree upon the gas velocity. In general, Vit ispreferred to make'use of a bed having an average particle size ranging from minus 10 to plus 80 mesh.

ln generati, it is undesirable to calcine raw barium ,carbonate'of the Vabove particle size.l Consequently, the barium carbonate itself should be of arelatively Vtine Vparticle size, usually being well below 100 mesh. This barium carbonate is then made up intopelletsor particles by mixing the barium carbonate, carbon black, and a suitable carbonaceous binder. Such binder must be capable Vof decomposing to evolve carbon or a gas, 'such' -as ,carbon dioxide, at the temperature of operation.

Typical binders are starch pasta-such -as pastes formed from wheat starch and other grain starches, includingV corn starch, rice starch, and various'other gluten-containing materials, glue, sugars, Syrups, molasses, tar, high boiling petroleum tlistillatesA or pitch and the like, and..var-ious other caibonaceous binders ofV analogous charactenpar-V ticularly Vthose compatible with water. The amount of binder-Which Vis usedv usually is not large andthus does .not-appreciably affect thercquiredcarbon contentoffthe barium Vcarbsnatc-carbon mixture. Usua1ly,.water is used junction with'the binder.

' ri iniicarboiiate, andthe binderare mixed Vwithwater theprod'uctionAof'lthese granulesor pellets, carbon, l

VAcessive.

in a suitable manner, for example, in a pug mill, to produce a plastic formable mass, and the product is extruded orY otherwise formed into` rods or like shape, usually having a diameter of ls to 1/4 inch. These rods are dried at a low temperature, for example, 100 to 150 C., in order to remove a major portion of the Water therefrom. After the drying operation, the extruded rods are found to lose'less than 0.1 Vpercent by weight of moisture when heated at 100 C. over aperiod of 24 hours. This amount Vis not objectionable. 'Howevenrlarger amounts tend to cause scaling or fusion in the 'calcination zone.

Thereafter, the granules are lightly crushed and screened .in order .to obtain particles of the size speciied above. p

ln the practice of the calcination, a tubular reactor adapted to hold a tiuidized bed is provided. An upwardly flowing stream of inert gas, such as nitrogen, is introduced .into the lower portion of the tube, and a body of previously calcined barium oxide granulesis introduced into the reactor to establish a dense uidized bed thereof. Such a bedhasawell defined upper level and is characterized by its high turbulence and its resemblance to boiling liquid.

The fluidized bed having been established, it is heated to calcination 4temperature and barium carbonate granules introduced. Thereafter, the barium carbonate granules are fed and barium oxide granules withdrawn continuously yOrl-intermittently. The composition of the bed remains high in barium oxide, at least 50 percent and usually running over ypercent byy weight of BaO, and thus .fusion is minimized by the high BaO content of the bed.

Ihetemperature .of operation of the calcination reactor. generallyis vestablished between S00 and ll00 C. .Whilehigher temperatures are operative, the problem of obtaining Vwalls of suitable metal which will stand up during operation and will conduct heat through to the reaction becomesmore complex. Furthermore, fusion becomes more serious. Using refractory materials of lconstructions which are especially adapted to stand the required temperature, temperatures as high as 1200 C., for even highencan be resorted to. However, the problem .ofsupplying heatto Vthe Vcalcination through a refractory Wallis diticnlt. Heat is Vsupplied byrheating the reactor through itsV walls `and/ or by pre-heating the uidizing gas. Wherethe ,barium oxide .is used in a cyclic process to produce'hydrogen peroxide, -itlias been found desirable to us'eaiiela'tivly Pure grade of carbon in the granules in Yorder togavoid `contamination by -metals or the like.

YO theilwise, these impuritiesfbuildup as the barium comlpofun'd proceeds ,through .aplurality of cycles. Con- Sequently,.relativelypure grades of carbon, such as lampblackand various .gas blacks, have been used. Equivalentamountgs (as to ,carbon content) of other carbo- .naceous reducing agents .may be used. Such agents include petroleum pitch, asphalt, tar, petroleum coke, or even icoal, Provided the amount of impurities is not ex- Y "The resultingrproduct,produced by the above described ,ilui'dizin' processgigs largely in theform of hard granules 'which are unusually Well 'bonded yapparently-due to slight loc'aljfusiojnl Where Ythecalcination has been carried out `t0'.Ilaiyly,high-degree of completeness, the granules contaifnoiily smalliamouuts ,of barium carbonate (less than lojper'e'ntjand usuallyf 1 to 5 percent by Weight of "theaQ and BaCQs Vinthecalcined product), depending uponthe degree o calcination,' together with some barium peroxide ,which "forfm whenthe barium oxide is al- 'lheprodu'ct also may contain some bariur'ng peroxide, the amountof carbon-present is held to Aa as hasQbeeiilpreviouslyexplained.

Topreyent bu ld p ohscalejto au undesirable thickness calcination reactor, the nitrogen n .P Qlcniah of oxygenV should notcoiit and carbon dioxide and, preferably, the nitrogen should l contain less than 0.1 to 0.2 percent of either Yof these com- Aherein contemplated. This apparatus comprises a nitrogen pre-heater which is connected to the fluidizing calciner 20. The nitrogen pre-heater comprises a heater tube 12 which may be of metal or other suitable material, and in which the pre-heating of the nitrogen actually is conducted. Surrounding this heater tube is ,a heating jacket furnace 14. Suitable sources of heat, such as gas burners land the like, are provided within the furnace 14. The calcinationreactor also comprises a metal tube 22 disposed in a furnace shell 24 which provides a chamber surrounding tube 22. Suitable burners (not shown), such as gas, powdered coal, or oil burners are disposed in this chamber to heat the (chamber and the interior of tube 22. Since these burners areV conventional in structure and operation, they require no discussion here.

The interior of tube 22 is coated with the barium oxidebarium carbonate coating described above. This coating Y is not shown in the drawing because its thinness is such that to become apparent, its dimension would have to be exaggerated unduly.

In the practice of the process, nitrogen is introduced at a rapid rate into the lower portion of the tube 12 and tiows upwardly through line 30 and into the lower portion of tube 12. This nitrogen ows upwardly through a fluidized bed of carbon granules or like relatively coarse inert materials (not shown) which are disposed in'tube 12. Additional carbon granules are added as needed from 1a charging device 32 through line 34. The lluidized bed is heated to an elevated temperature, usually above 500 C. and frequentlyas high as 1000 C., by powdered coal, oil or gas burners (not shown) disposed in the gas furnace 14, and thereby converts oxygen and carbon dioxide in the nitrogen to carbon monoxide. The heated nitrogen escapes from the top of the pre-heater through line 36 and is discharged into a cyclone separator 38 to separate dust. This dust is collected in the bottom of the separator and may be removed from time to time through the bottom outlet 40.

The nitrogen is Vremoved from the cyclone separator through line 50 and is led to the bottom of tube 22 which tapers to a conical inlet. Barium carbonate granules are fed from a supply bin 52 into a Vhopper 54 and thence through a rotating star valve k56 intoV line 58. This line discharges into line 50 and, thus, the hot nitrogen entering the tube 22 picks up the barium carbonate pellets and carries them into the tube 22. A fluidized bed of barium oxide or =a mixture of barium carbonate and barium oxide is maintained in tube 272, the upper level of this fluid bed being at the level of the overflow pipe 60. 'Ilhis overflow pipe discharges the calcined product. In order to permit the nitrogen to by-pass the pre-heater and/or the pellet feeding line, by-pass linesf62, 64, and 66 are provided.,

Effluent-gases from the reaction escape .above the fluidl bed through the top of the tube, as indicated in the drawing.

The practice 4of this process is especially advantageous since it tends to avoid fusion of the barium carbonate during calcination. Preferably, the fiuidized bed isV so operated that it is largely barium oxide. It will be understood that inasmuch as the bed itself is turbulent, its composition is substantially uniform, particularly in the upper portions thereof. As =a consequence of the calcination, lthe lfluid bed will contain substantial portions of barium oxide 'and barium carbonate togetherl with some barium peroxide. There is4 also present a concentration of carbo- `naceous reducing agent; depending upon the amount of such agent incorporated in thebariumcarbonate product introducedinto the bed.v L n n p In calcining barium carbonate according to this meth-` od, the uid bed may be operated ina manner Vsuch as to achieve any degree of calcinationV from 10.to 100 percent. On the other hand, best results are obtained when `the barium oxide content of the bed is in excess of 50 percent of theV B'aO content of the barium carbonate going into the uidized bed. This method affords a convenient method of avoiding the diiiiculties encountered inconventional calcining processes which appear to be due to a formation of a barium oxide-barium ca'rbonate eutectic. Thus, there is a definite indication that such eutectic melts at a much lower temperature than do either barium oxide or barium carbonate and consequently the eutectic which may'be formed during calcination tends to promote fusion ofthe product. In contrast, the present process affords a convenient method wherein the barium carbonate is added to a calcining bed which containsa large amount of barium oxide. Thus, the composition of the bed with respect to barium oxide and barium carbonate is above that at which the barium oxide# barium Acarbonate eutectic has been regarded to exist. Because the overall composition of the bed is such 'that the barium oxide content thereof is above that at which the low melting barium oxide-barium carbonate eutectic is formed, fusion is minimized. For this reason it is found advantageous to conduct `the calcination under conditions such that the bed contains at least 50 lto 75 percent, and preferably in excess of 90 percent, of BaO, based upon the total amount of BaO and barium carbonate in the fluidized bed. p

It will be understood, of course, that the process may be lconducted in a plurality of stages. Thus, two or more fluidized beds of barium oxide and bariumcarbonate may be provided in order Vto elect a partial calcination in one bed and a further calcination in another bed. In such a case, the degree of calcination in the rstbed may be'quite incomplete and the bed may contain as little as 30 percent barium/oxide, based upon the total BaO entering the bed. However, even in such cases it is found most advantageous to conduct theoperation so that the major portion of the BaO (more than 1/z) in the iluidized bed is present in the'bed as barium oxide. In optimum operation, the beds may contain 90 to 98 percent ofv barium oxide, base upon the total BaO in the bed. Whilebeds of higher barium oxide content may be operated, this isV usually impractical. Y p 'I'he following is an illustrative example of thisembodiment of the invention:

.n Example 'l The apparatus illustrated in Fig. 1 was used. In this test, the calcination reactor comprised a metal tube 22 having a diameter of 4 inches at the top of the bed level and adiameter of 3 inches at the end of the tube where it was tapered to provide the inlet for the reactants. The distance between the end of the tube and the top of the bed was 56 inches. The nitrogen pre-heater constituted a 4-in'chdiameter tube112 which wasr36 inheslong. The interior of the tube 22 is lined with a thin barium oxide-barium carbonatecoating in which `the mole ratio of BaCOs to BaO is 1.9,", This may be applied bya prestage of the process.

p In a typical operation, 100 parts by weight of finely divided barium carbonate having a particle size of minus `100 to plus 300 mesh, 7 parts by weight of carbon lamp- A black, and one part by weight of an aqueous paste of Vwater suicient to make a stiff plastic mass.

sirm'lar nonreactive gas. iused, it has-been found that carbon black Commonly in- 7 andthe crushed product was screened tsp-.obtain a productransing from mnus14'to p1us30- meshin size.

.In the .calcination :nitrogen was introduced into .the bottom -of the-nitrogen pre-heater and passed through a uidized bed of graphite granules having a .particle ysize of Vabout minus 14` to plus :80 mesh. The temperature of :the nitrogen gas escaping 'from this` bed was approximately 540 C. The temperature ofthe bed was approxinrately 85019 900 C. Consequently, the oxygen and carbon vdioxide in the nitrogen were almost quantitatively `converted to carbon monoxide. (Note that the nitrogen entering the fluid carbon bed contained.0.4 to 0,8 Vpercentby volume of oxygen and only a Yminute amountof carbon dioxide.) v

'The resulting heated nitrogen containing less than 0.2

Percent .oxygen was fed into the calcination reactor at a rate lofZQtfl--to 265 cubic feet per hour, `computed at 760 millimeters pressure land `70 F. About 20 pounds of previouslycalcined barium carbonate ygranules of the type described above4 and containing in excess of 95 percent B a() -were dumped vinto the Areactor and a fluidized bed wasestablished in the reactor. The temperature of .this bed was maintained throughout the run at about -945 to 965 C. During the run, wthe barium carbonate granules were fed into the nitrogen at ka rate of 13 to 14 pounds per hour. The operation was continued over a period of 18 hours .and the product withdrawncontinuously. This product contained 94 to l99 percent4 by weight of barium oxide. No scale deposit was apparent on the wall. Only a very small amount of Solids fed to the reactor were 'carried oil as solids in the gas stream in the form of dust.

In order to develop the desired protective coating on the metal walls, theV oxygen content in the nitrogen used in thezrst run of this character is Yheld `at about 0.5 Apercent'by volume for 30 minutes., T his'may beaccomplished by using inert granules rather than graphite ,granules in the nitrogen pre-heater during such period. Thereafter, the-'oxygen content of the nitrogen is reduced to below 0.1 to 0.2 percent.

As has been previously explained, it is found preferable to use nitrogen as the uidizing gas. Air and carbon dioxide vare not satisfactory for this purpose since .eachtends to reverse the reaction and to cause fusion.

VCarbon monoxide may b e--used where the temperature of .the calcination is above about 1050 C. However, this high temperature sometimes is objectionable because it is dicult to obtain metal which will serve as satisfactory tubes for holding the reaction mixture. Other inert .or nonreactive gases may be used, as will be understood by those skilled in the art. A

rAccording to ,a further embodiment of the invention, barium carbonate may be calcined in a stream of a gaseous hydrocarbon. The best hydrocarbon for this purpose is methane. propane, .butane, propylene, ethylene, butylene, and the like may be used. Suchpa process may be conducted using methane Yor like hydrocarbon in lieu of nitrogenor When suchV ahydrocarbon is v,corpcn'atedin Vthe particles, may be partially or completely dispensed with. Thus, it has been-discovered that during r`the reaction-the methane or'like hydrocarbon cracks to depositcarbon on the barium carbonate granules. This is highly surprising-since it might Well be expected thatV Vif lthe methane cracked during the reaction, the carbon might well deposit `upon all portions of the reactor Arather However, other hydrocarbons, such as ethane,

with it and thus the Aobjectionable eiect or oxygen can be minimized. Moreoyeneven partial decomposition or vcalcination of barium l.carbonate is permitted when methane is used. VAs has been shown above, the carbon tends to reduce fusion, and Vwhen -no carbonis. added to the particles, serious fusion-results during calculation. While -less .than the stoiehiometric amount (6 percent of-,the barium carbonate) may be used, the tendency toward fusion gradually increases and becomes quite serious when'only 3 or 4 percent by `Weight of-carbon, based upon the barium carbonate, is used. When methane is used, however, this does not appear -to be the case.`

' Quite probably, the fusion is dueV to the presence of barium oxide which forms abarium `oxide eutectic. On the other hand, the'bariumoxide is not formed at the relatively low calcination temperatures used inthe practice of thisprocess, for example,-800 to 1200 C. (usually below 103,0" C.) unless carbon is present. When methane or like gaseous hydrocarbon is used as the primary source of. carbon, it follows that the calcination can only occur where the carbon has .been deposited by virtue of methane cracking.

Hydrocarbons other than methane, including ethane,

propane, butane, vapors ofpetroleiun naphtha, petroleum pitch, benzene and like products which, upon heating at the elevated temperatures herein contemplated will crack to form carbon, may be used according to the present invention. .A The calcination may be eected using both methane, or like hydrocarbon, and elemental carbon. In such a case, aV deficiency of carbon (less than 6 percent, for example'l to 4 percent by Weight) may be incorporated in the granules prior to calcination, and the hydrocarbon used toY supply the balance of the carbon.

The following examples are illustrative of the process involving use of methane: i

Example Il The apparatus usedrwas that described in Example I except that methane was fed, without pre-heating, into Vthe reactor in lieu of nitrogen. Granules were prepared Vfed into the reactor-in lieu ofnitrogen at a rate of 285 cubic feet per hour, measured at a pressure of 760 millimeters and a temperature of 70 F. The temperature of the reaction bed was maintained at approximately 975 C. during the run, and the barium oxide content of the bed remained at 90 to 92 percent by weight of the bed.

' The calcination was carried out for a period of 5 hours,

and the product withdrawn contained 90 to -92 percent of barium oxide. Thebed did not fuse Vor stick during the Y Y Example Ill I Y* Y Using the apparatusdescribed in Example I, a iluidized bed of baked bariumpcarbonate granules having a par- Vticle size such that 100 percent passed through 14 mesh and-remained onr30 meshwas established. Y'These granules were prepared as described in Example I except that 4 parts -by weight of carbon and 1 part by; weight-of wheat starch were used per 100 parts by weight ofbarium carwhich is formed'by cracking of thfemethane is deposited- Viny the pores of the Vbarium carbonate granules and in such intimate contactV that the introductionV of Y methane eifectively servesthe sameY purpose as the incorporation of tneuirzi-negas,ihe .methane tends to react the ow atlF. and 760 Ymillimeters pressure.

H t 'bonate Vthan upon the bariumcarbonate. Actually, the carbonY ,l

Thesegranules were fed to the reactor at a rateof 14.42pounds per* hour, Vaccording to the process of Example I. Nitrogen pre-heated to a temperature of L approximately 550 C. flowing-at a rate .05200 to 285 cubic feet per hour and measured at 760, was mixed with a stream orpr cold methane ilowing at. a rate` of 5 6 cubic feet-per h our. These gasV flows weremeasured in terms of The resultingV gas VYmixture was-fed into-the bottomrof the reactor as in Example I, and was used to maintain the uidized bed. The operation was continued over a period of 7 hours and the resulting product was continually withdrawn during the run. This product contained 92 to 97 percent BaO.

Example I V The procedure in this experiment was substantially that described in Example I, and the equipment was the same. The feed was a mixture of 7 parts by weight of carbon, one part by Weight of wheat paste, and 100 parts by weight of barium carbonate, the particles which were greater in size than 14 mesh or less than 30 mesh being screened out. The feed of these granules was 10.4 pounds per hour. The nitrogen was heated in the pre-heater at a temperature of about 500 C. and fed into the reactor at a rate of 225 cubic feet per hour. Prior to introducing the nitrogen into the reactor, it was mixed with cold methane introduced at a rate of 50 cubic feet per hour. These gas flows are expressed in terms of their volume at 760 millimeters pressure at 70 F. This mixture was fed into the bottom of the reactor and used to establish the Huidized bed. The temperature of the reaction bed was maintained at 950 C. throughout the run. The run was continued for a period of 3% hours at these conditions, and the product which was withdrawn continually during the run contained 93 to 95 percent BaO.

The barium carbonate used in the runs was substan- `tially all barium carbonate containing small amounts,

scribed above or even a finely divided mixture of barium oxide, barium carbonate, and carbon may be placed on a rotary hearth or like heating apparatus, the exposed surfaces of which may be coated with barium oxide or barium oxide-barium carbonate as herein contemplated, and calcined in a stream of inert gas. To avoid or minimize fusion, itis usually desirable to mix the barium carbonate with previously calcined granules. Thus, a portion of the calcined product may be recycled and mixed with barium carbonate entering the furnace, as has been explained above. In such a case, the barium oxide content of the mixture normally will exceed 50 percent of the BaO content of the mixture undergoing calcination. By such means, fusion due to the production of a low melting barium oxide eutectic may be minimized. Radiant heat may be used to heat the hearth in such a process.

Moreover, the barium carbonate-carbon mixture may be prepared in other ways. For example, barium carbonate granules such as prepared according to Examples II or III, or other barium carbonate compositions which contain little or no carbon or like hydrocarbon, may be subjected to a pre-treatment with methane at cracking temperatures, for example, 400 to 800 C., in order to deposit carbon upon the barium carbonate. Such granules may be calcined in the usual manner, for example, according to the method shown in Example I.

Barium oxide which is produced by this process may be used for many purposes. It may be reacted with air to produce various barium salts. It also may be hydrated to produce barium hydroxide.

According to a further embodiment, barium oxide granules pre-heated to a temperature above calcination Ytive materials of construction.

but belowvfusion temperatures may be introduced into a tluidized bed such as that described in Examples I to 1V. By this means, additional heat may be introduced into the calcining chamber, thus reducing the amount of heat which must pass through the walls of the chamber and permitting use of more refractory and less heat conduc- The barium carbonate granules also may be pre-heated to reaction temperature, or somewhat below, for the same purpose.

The above described reactor is especially useful for calcination of barium carbonate. However, it may be used to react barium oxide with oxygen to produce barium peroxide according to methods described in application for United States Letters Patent Serial No. 279,787, led April 1, 1952, of Henry W. Rahn, John W. Moore, and Charles I. Sindlinger.

Although the present invention has been described with reference to the specific details of certain embodiments thereof, it is not intended that such details shall be regarded as limitations upon the scope of the invention ,except insofar as included in the accompanying claims.

This application is a continuation-in-part of our copending application Serial No. 279,786, tiled April 1, 1952.

What is claimed:

1. In the calcination of barium carbonate by establishing a uidized bed comprising barium carbonate and carbon in an upwardly rising stream of inert gas, said bed being disposed in a reactor having a metal wall, while heating the bed by transfer of heat into the reactor from a point exteriorly thereof through said metal wall, the improvement which comprises heating said bed through a metal wall which is coated on the side in contact with the uidized bed with an adherent coating of a member of the group consisting of barium oxide and mixtures of barium oxide and barium carbonate, said coating being less than Vs inch in thickness.

2. In the calcination of barium carbonate by establishing a uidized bed comprising barium carbonate and carbon in an upwardly rising stream of inert gas, said bed being disposed in a reactor having a metal wall, while heating the bed by transfer of heat into the reactor from a point exteriorly thereof through said metal Wall, the improvement which comprises heating said bed through a metal wall which is coated on the side in contact with the fluidized bed with an adherent of a mixture comprising barium oxide and barium carbonate, said coating being less than 1/s inch in thickness.

References Cited in the tile of this patent UNITED STATES PATENTS 339,360 Batho Apr. 6, 1886 974,921 Rollin Nov. 8, 1910 1,047,077 Kirchner Dec. 10, 1912 1,243,190 Kremers Oct. 16, 1917 1,852,162 Harris et al. Apr. 5, 1932 1,870,034 Brophy et al Aug. 2, 1932 FOREIGN PATENTS 908 Great Britain 1878 OTHER REFERENCES Rules of Practice of U. S. Patent Oce, Jan. 1, 1953, p. 122.

McPherson and Henderson book General Chemistry, 3rd ed., page 596. Ginn and Co., New York. 

1. IN THE CALCINATION OF BARIUM CARBONATE BY ESTABLISHING A FLUIDIZED BED COMPRISING BARIUM CARBONATE AND CARBON IN AN UPWARDLY RISING STREAM OF INERT GAS, SAID BED BEING DISPOSED IN A REACTOR HAVING A METAL WALL, WHILE HEATING THE BED BY TRANSFER OF HEAT INTO THE REACTOR FROM A POINT EXTERIORLY THEREOF THROUGH SAID METAL WALL, THE IMPROVEMENT WHICH COMPRISES HEATING SAID BED THROUGH A METAL WALL WHICH IS COATED ON THE SIDE IN CONTACT WITH THE FLUIDIZED BED WITH AN ADHERENT COATING OF A MEMBER OF THE GROUP CONSISTING OF BARIUM OXIDE AND MIXTURES OF BARIUM OXIDE AND BARIUM CARBONATE, SAID COATING BEING LESS THAN 1/8 INCH IN THICKNESS. 